JP2008546690A5

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Publication number: JP2008546690A5
Application number: JP2008516890A
Authority: JP
Filing date: 2006-05-24
Publication date: 2009-07-09

Description

ここで図６〜７を参照し、液相供給物流を反応ゾーン２８内に導入するための代替のシステムを説明する。この態様において、供給物流は４つの異なる高さで反応ゾーン２８内に導入する。各高さは、それぞれの供給物分配システム７６ａ，ｂ，ｃ，ｄを備える。各供給物分配システム７６は、主供給管路７８および連結管（manifold）８０を含む。各連結管８０は、容器シェル２２の反応ゾーン２８内に延びる挿入管路８６，８８にそれぞれ連結した少なくとも２つの出口８２，８４を備える。各挿入管路８６，８８は、供給物流を反応ゾーン２８内に放出するためのそれぞれの供給物開口８７，８９を与える。供給物開口８７，８９は、好ましくは、実質的に同様の直径約７センチメートル未満、より好ましくは約０．２５から約５センチメートルの範囲、および最も好ましくは０．４から２センチメートルの範囲を有する。各供給物分配システム７６ａ，ｂ，ｃ，ｄの供給物開口８７，８９は、反対の方向で供給物流を反応ゾーン２８内に導入するように直径方向において反対側にあることが好ましい。さらに、隣接する供給物分配システム７６の、直径方向において反対側の供給物開口８７，８９は、相対的に互いに９０度回転させた方向であることが好ましい。操作においては、液相供給物流は、主供給物管路７８に充填し、続いて連結管８０に入る。連結管８０は、供給物流を、反応器２０の反対側で供給物開口８７，８９を経由して同時に導入するために均等に分配する。 With reference now to FIGS. 6-7, an alternative system for introducing a liquid phase feed stream into reaction zone 28 will be described. In this embodiment, the feed stream is introduced into the reaction zone 28 at four different heights. Each height includes a respective feed distribution system 76a, b, c, d. Each feed distribution system 76 includes a main supply line 78 and a manifold 80. Each connecting tube 80 includes at least two outlets 82, 84 connected to insertion conduits 86, 88 that extend into the reaction zone 28 of the vessel shell 22, respectively. Each insertion line 86, 88 provides a respective feed opening 87, 89 for discharging the feed stream into the reaction zone 28. Feed openings 87, 89 are preferably substantially less than about 7 centimeters in diameter, more preferably in the range of about 0.25 to about 5 centimeters, and most preferably in the range of 0.4 to 2 centimeters. Have a range. The feed openings 87, 89 of each feed distribution system 76a, b, c, d are preferably diametrically opposed so as to introduce the feed stream into the reaction zone 28 in the opposite direction. Furthermore, the feed openings 87 , 89 on the opposite diametrical side of adjacent feed distribution systems 76 are preferably in a direction that is rotated 90 degrees relative to each other. In operation, the liquid phase feed stream fills the main feed line 78 and then enters the connecting line 80. The connecting tube 80 distributes the feed stream evenly for simultaneous introduction on the opposite side of the reactor 20 via feed openings 87, 89.

本発明のある態様において、反応ゾーン内に導入される全易酸化性化合物の少なくとも約１０質量パーセントを酸化剤スパージャー経由で導入することが好ましく、より好ましくは易酸化性化合物の少なくとも約４０質量パーセントを反応ゾーン内に酸化剤スパージャー経由で導入し、そして最も好ましくは易酸化性化合物の少なくとも８０質量パーセントを反応ゾーン内に酸化剤スパージャー経由で導入する。易酸化性化合物の全部または一部を反応ゾーン内に酸化剤スパージャー経由で導入する場合、反応ゾーン内に導入される全分子酸素の少なくとも約１０質量パーセントを同じ酸化剤スパージャー経由で導入することが好ましく、より好ましくは、分子酸素の少なくとも約４０質量パーセントを同じ酸化剤スパージャー経由で導入し、そして最も好ましくは分子酸素の少なくとも８０質量パーセントを同じ酸化剤スパージャー経由で導入する。易酸化性化合物の相当多くの部分が反応ゾーン内に酸化剤スパージャー経由で導入される場合、１つ以上の温度感知装置（例えば熱電対）を酸化剤スパージャー内に配置することが好ましい。このような温度検知器を採用して、酸化剤スパージャー内の温度が危険な程に高くならないことを確認する助けとすることができる。 In certain embodiments of the present invention, it is preferred to introduce at least about 10 weight percent of all oxidizable compounds introduced into the reaction zone via an oxidant sparger, more preferably at least about 40 weight of oxidizable compounds. Percent is introduced into the reaction zone via an oxidant sparger, and most preferably at least 80 weight percent of the oxidizable compound is introduced into the reaction zone via an oxidant sparger. When all or part of the oxidizable compound is introduced into the reaction zone via an oxidant sparger, at least about 10 weight percent of all molecular oxygen introduced into the reaction zone is introduced via the same oxidant sparger. it is preferred, more preferably, at least about 40 weight percent of the molecular oxygen introduced via the same oxidant sparger, and most preferably introducing at least 80 weight percent of the molecular oxygen through the same oxidant sparger. Where a significant portion of the oxidizable compound is introduced into the reaction zone via the oxidant sparger, it is preferred to place one or more temperature sensing devices (eg, thermocouples) within the oxidant sparger. Such a temperature detector can be employed to help ensure that the temperature in the oxidant sparger does not become dangerously high.

典型的には、Ｔ−ｍａｘ水平方向スライスは、反応媒体３６の中心近傍に位置することになり、一方Ｔ−ｍｉｎ水平方向スライスは、反応媒体３６の底部近傍に位置することになる。好ましくは、Ｔ−ｍｉｎ水平方向スライスは、１５の最も下の水平方向スライスのうち最下の１０の水平方向スライスの１つである。最も好ましくは、Ｔ−ｍｉｎ水平方向スライスは、１５の最も下の水平方向スライスのうち最下の５の水平方向スライスの１つである。例えば、図２８は、Ｔ−ｍｉｎ水平方向スライスを、反応器２０の底部から２番目の水平方向スライスとして示す。好ましくは、Ｔ−ｍａｘ水平方向スライスは、３０の離散水平方向スライスのうち中央の２０の水平方向スライスの１つである。最も好ましくは、Ｔ−ｍａｘ水平方向スライスは、３０の離散水平方向スライスのうち中央の１４の水平方向スライスの１つである。例えば、図２８は、Ｔ−ｍａｘ水平方向スライスを、反応器２０の底部から２０番目の水平方向スライス（すなわち中央の１０の水平方向スライスの１つ）として示す。Ｔ−ｍｉｎ水平方向スライスとＴ−ｍａｘ水平方向スライスとの間の垂直方向の間隔は、少なくとも約２Ｗであることが好ましく、より好ましくは少なくとも約４Ｗ、および最も好ましくは少なくとも６Ｗである。Ｔ−ｍｉｎ水平方向スライスとＴ−ｍａｘ水平方向スライスとの間の垂直方向の間隔は、少なくとも約０．２Ｈであることが好ましく、より好ましくは少なくとも約０．４Ｈ、および最も好ましくは少なくとも０．６Ｈである。 Typically, the T-max horizontal slice will be located near the center of the reaction medium 36, while the T-min horizontal slice will be located near the bottom of the reaction medium 36. Preferably, the T-min horizontal slice is one of the bottom 10 horizontal slices of the 15 bottom horizontal slices. Most preferably, the T-min horizontal slice is one of the bottom 5 horizontal slices of the 15 bottom horizontal slices. For example, FIG. 28 shows a T-min horizontal slice as the second horizontal slice from the bottom of the reactor 20. Preferably, the T-max horizontal slice is one of the central 20 horizontal slices of the 30 discrete horizontal slices. Most preferably, the T- max horizontal slice is one of the central 14 horizontal slices of the 30 discrete horizontal slices. For example, FIG. 28 shows a T-max horizontal slice as the 20th horizontal slice from the bottom of the reactor 20 (ie, one of the central 10 horizontal slices). The vertical spacing between the T-min horizontal slice and the T-max horizontal slice is preferably at least about 2W, more preferably at least about 4W, and most preferably at least 6W. The vertical spacing between the T-min horizontal slice and the T-max horizontal slice is preferably at least about 0.2H, more preferably at least about 0.4H, and most preferably at least about 0.1. 6H.

溶媒または易酸化性化合物のいずれの起源でも、商業的用途の変換では、全体的な反応活性のレベルを得るために採用される温度、金属、ハロゲン、ｐＨで測定される反応媒体の酸性度、水濃度の具体的な組合せが幅広くばらつくことに関わらず、炭素酸化物の生成が全体的な反応活性のレベルに強く関係することを発明者らは見出した。発明者らは、キシレンの部分酸化について、反応媒体の中間高さ、反応媒体の底部、および反応媒体の頂部でのトルイル酸の液相濃度を用いて全体的な反応活性のレベルを評価することが有用であることを見出した。 For either commercial or oxidizable compound origin, in conversion for commercial use, the reaction medium acidity measured in temperature, metal, halogen , pH employed to obtain the overall level of reaction activity. The inventors have found that the formation of carbon oxides is strongly related to the overall level of reaction activity, regardless of the wide variation in specific combinations of water concentrations. We evaluate the overall level of reaction activity for partial oxidation of xylene using the intermediate height of the reaction medium, the bottom of the reaction medium, and the liquid phase concentration of toluic acid at the top of the reaction medium. Found useful.

本発明をその好ましい態様を特に参照して詳細に説明したが、本発明の精神および範囲に含まれる範囲で変更および改変を行うことが可能であることが理解されよう。
［１］（ａ）芳香族化合物を酸化反応器に供給すること、
（ｂ）前記酸化反応器に含まれる多相反応媒体の液相における前記芳香族化合物の少なくとも一部の、二酸化炭素，一酸化炭素，および／または酢酸メチルを生成する酸化によって粗テレフタル酸を生成させること、ならびに
（ｃ）前記酸化の間、以下の特定範囲の以下の操作比率：
（ｉ）生成される炭素酸化物のモル数の、供給される前記芳香族化合物のモル数に対する比を、約０．０２：１から約０．２４：１の範囲に維持すること、
（ｉｉ）生成される前記二酸化炭素のモル数の、供給される前記芳香族化合物のモル数に対する比を、約０．０１：１から約０．２１：１の範囲に維持すること、
（ｉｉｉ）生成される前記一酸化炭素のモル数の、供給される前記芳香族化合物のモル数に対する比を、約０．００５：１から約０．０９：１の範囲に維持すること、
（ｉｖ）生成される前記酢酸メチルのモル数の、供給される前記芳香族化合物のモル数に対する比を、約０．００５：１から約０．０９：１の範囲に維持すること、
のうち１つ以上を維持することを含む方法。
［２］生成される炭素酸化物のモル数の、供給される前記芳香族化合物のモル数に対する前記比を、約０．０２：１から約０．２４：１の範囲に維持する、上記［１］に記載の方法。
［３］生成される前記二酸化炭素のモル数の、供給される前記芳香族化合物のモル数に対する前記比を、約０．０１：１から約０．２１：１の範囲に維持する、上記［１］に記載の方法。
［４］生成される前記一酸化炭素のモル数の、供給される前記芳香族化合物のモル数に対する前記比を、約０．００５：１から約０．０９：１の範囲に維持する、上記［１］に記載の方法。
［５］生成される前記酢酸メチルのモル数の、供給される前記芳香族化合物のモル数に対する前記比を、約０．００５：１から約０．０９：１の範囲に維持する、上記［１］に記載の方法。
［６］生成される炭素酸化物のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０２：１から約０．２４：１の範囲に維持し、生成される前記二酸化炭素のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０１：１から約０．２１：１の範囲に維持し、生成される前記一酸化炭素のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．００５：１から約０．０９：１の範囲に維持し、生成される前記酢酸メチルのモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．００５：１から約０．０９：１の範囲に維持する、上記［１］に記載の方法。
［７］前記操作比率のうち少なくとも１つを少なくとも１２時間維持する、上記［１］に記載の方法。
［８］前記操作比率のうち少なくとも２つを少なくとも１２時間維持する、上記［１］に記載の方法。
［９］前記操作比率のうち少なくとも３つを少なくとも１２時間維持する、上記［１］に記載の方法。
［１０］前記操作比率の全てを少なくとも１２時間維持する、上記［１］に記載の方法。
［１１］生成される炭素酸化物のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０５：１から約０．１９：１の範囲に維持し、生成される前記二酸化炭素のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０４：１から約０．１６：１の範囲に維持し、生成される前記一酸化炭素のモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０１５：１から約０．０５：１の範囲に維持し、生成される前記酢酸メチルのモル数の供給される前記芳香族化合物のモル数に対する前記比を約０．０１：１から約０．０７：１の範囲に維持する、上記［１］に記載の方法。
［１２］前記操作比率の全てを少なくとも３６時間維持する、上記［１］に記載の方法。
［１３］前記芳香族化合物が、パラキシレン、メタキシレン、パラトルアルデヒド、メタトルアルデヒド、パラトルイル酸、メタトルイル酸、アセトアルデヒド、およびこれらの２種以上の組合せからなる群から選択される、上記［１］に記載の方法。
［１４］前記芳香族化合物がパラキシレンである、上記［１］に記載の方法。
［１５］前記酸化によって前記芳香族化合物の少なくとも約５０モルパーセントをテレフタル酸に変換させる、上記［１］に記載の方法。
［１６］前記酸化によって前記芳香族化合物の少なくとも約１０質量パーセントが前記反応媒体中で固体を形成する、上記［１］に記載の方法。
［１７］前記酸化が熱を発生させ、前記酸化によって発生した熱の約５０パーセント未満を熱交換面により前記反応媒体から除去する、上記［１］に記載の方法。
［１８］酸化剤流を前記酸化反応器に供給することを含み、前記酸化剤流が約５０モルパーセント未満の分子酸素を含む、上記［１］に記載の方法。
［１９］前記酸化反応器が気泡塔反応器である、上記［１］に記載の方法。
［２０］前記反応媒体が固相、液相および気相を含む、上記［１］に記載の方法。
［２１］前記芳香族化合物がパラキシレンであり、前記酸化によって前記パラキシレンの少なくとも約９０モルパーセントをテレフタル酸に変換し、前記酸化によって前記パラキシレンの少なくとも約５０質量パーセントが前記反応媒体中に固体テレフタル酸を形成し、前記酸化によって熱が発生し、前記酸化によって発生した熱の約３０パーセント未満を熱交換面により前記反応媒体から除去し、前記方法が、酸化剤流を前記反応器に供給することを含み、前記酸化剤流が約１５から約３０モルパーセントの分子酸素を含む、上記［１］に記載の方法。
［２２］前記反応媒体の液相中のパラトルイル酸の濃度が約８，０００ｐｐｍｗ未満である、上記［１］に記載の方法。
［２３］スラリーを前記酸化反応器から取出すことをさらに含み、前記スラリーが液体母液および前記粗テレフタル酸の固体粒子を含み、前記スラリーの代表試料が、組合された固体および液体のスラリー成分に基づいて、以下の特徴：
（ｖ）約１，５００ｐｐｍｗ未満のイソフタル酸（ＩＰＡ）を含む、
（ｖｉ）約５００ｐｐｍｗ未満のフタル酸（ＰＡ）を含む、
（ｖｉｉ）約５００ｐｐｍｗ未満のトリメリット酸（ＴＭＡ）を含む、
（ｖｉｉｉ）約２，０００ｐｐｍｗ未満の安息香酸（ＢＡ）を含む、
のうち１つ以上を有する、上記［１］に記載の方法。
［２４］前記酸化反応器からの乾燥オフガス中の前記二酸化炭素の量が約０．１から約１．５モルパーセントの範囲であり、前記酸化反応器からの乾燥オフガス中の前記一酸化炭素の量が約０．０５から約０．６モルパーセントの範囲であり、前記酸化反応器からの乾燥オフガス中の前記分子酸素の量が約０．１から約６モルパーセントの範囲である、上記［１］に記載の方法。
［２５］前記反応媒体を経由した芳香族化合物のモル残存比率が、約９８から約９９．９パーセントの範囲である、上記［１］に記載の方法。
［２６］前記酸化を、コバルトを含む触媒系の存在下で行う、上記［１］に記載の方法。
［２７］前記触媒系が、臭素およびマンガンをさらに含む、上記［１７］に記載の方法。
［２８］前記粗テレフタル酸の実質的部分が固体粒子として存在し、前記粗テレフタル酸粒子の代表試料が、以下の特徴：
（ｉｘ）約１２ｐｐｍｗ未満の４，４−ジカルボキシスチルベン（４，４−ＤＣＳ）を含む、
（ｘ）約８００ｐｐｍｗ未満のイソフタル酸（ＩＰＡ）を含む、
（ｘｉ）約１００ｐｐｍｗ未満の２，６−ジカルボキシフルオレノン（２，６−ＤＣＦ）を含む、
（ｘｉｉ）３４０ナノメートルでの透過率パーセント（％Ｔ ₃₄₀ ）が約２５を超える、
のうち１つ以上を有する、上記［１］に記載の方法。
［２９］前記粗テレフタル酸の実質的部分が固体粒子として存在し、前記粗テレフタル酸粒子の代表試料が、本明細書で定義する時限溶解試験を受けた際に、１分間でＴＨＦ中に少なくとも約５００ｐｐｍの濃度に溶解する、上記［１］に記載の方法。
［３０］前記粗テレフタル酸の実質的部分が固体粒子として存在し、前記粗テレフタル酸の代表試料の、本明細書で定義する時限溶解モデルにより決定される時間定数“Ｃ”が約０．５逆数分を超える、上記［１］に記載の方法。
［３１］前記粗テレフタル酸の少なくとも一部を二次酸化反応器において酸化させることをさらに含む、上記［１］に記載の方法。
［３２］（ａ）芳香族化合物を酸化反応器に供給すること、
（ｂ）前記芳香族化合物の少なくとも一部を、前記酸化反応器に含まれる多相反応媒体の液相において酸化させることによって粗テレフタル酸を生成させること、ならびに
（ｃ）前記酸化の間、前記芳香族化合物のモル残存比率を約９８パーセント超に維持すること、
を含む方法。
［３３］前記モル残存比率を約９８．５から約９９．８パーセントの範囲に維持する、上記［３２］に記載の方法。
［３４］前記モル残存比率を約９９から約９９．７パーセントの範囲に維持する、上記［３２］に記載の方法。
［３５］前記芳香族化合物が、パラキシレン、メタキシレン、パラトルアルデヒド、メタトルアルデヒド、パラトルイル酸、メタトルイル酸、アセトアルデヒド、およびこれらの２種以上の組合せからなる群から選択される、上記［３２］に記載の方法。
［３６］前記酸化によって前記芳香族化合物の少なくとも約５０モルパーセントをテレフタル酸に変換させる、上記［３２］に記載の方法。
［３７］前記酸化によって前記芳香族化合物の少なくとも約１０質量パーセントが前記反応媒体中で固体を形成する、上記［３２］に記載の方法。
［３８］前記酸化が熱を発生させ、前記酸化によって発生した熱の約５０パーセント未満を熱交換面により前記反応媒体から除去する、上記［３２］に記載の方法。
［３９］酸化剤流を前記酸化反応器に供給することを含み、前記酸化剤流が約５０モルパーセント未満の分子酸素を含む、上記［３２］に記載の方法。
［４０］前記モル残存比率を少なくとも１２時間維持する、上記［３２］に記載の方法。
［４１］前記酸化反応器が気泡塔反応器である、上記［３２］に記載の方法。
［４２］前記反応媒体が固相、液相および気相を含む、上記［３２］に記載の方法。
［４３］前記芳香族化合物がパラキシレンであり、前記酸化によって前記パラキシレンの少なくとも約９０モルパーセントをテレフタル酸に変換させ、前記酸化によって前記パラキシレンの少なくとも約５０質量パーセントが前記反応媒体中に固体テレフタル酸を形成し、前記酸化によって熱が発生し、前記酸化によって発生した熱の約３０パーセント未満を熱交換面により前記反応媒体から除去し、前記方法が、酸化剤流を前記反応器に供給することを含み、前記酸化剤流が約１５から約３０モルパーセントの分子酸素を含み、前記モル残存比率を少なくとも３６時間維持する、上記［３２］に記載の方法。
［４４］前記反応媒体の液相中のパラトルイル酸の濃度が約８，０００ｐｐｍｗ未満である、上記［３２］に記載の方法。
［４５］前記酸化を、コバルト、臭素およびマンガンを含む触媒系の存在下で行う、上記［３２］に記載の方法。
［４６］前記粗テレフタル酸の少なくとも一部を二次酸化反応器において酸化させることをさらに含む、上記［３２］に記載の方法。 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
[1] (a) supplying an aromatic compound to the oxidation reactor;
(B) Producing crude terephthalic acid by oxidation of producing at least part of the aromatic compound in the liquid phase of the multiphase reaction medium contained in the oxidation reactor to produce carbon dioxide, carbon monoxide, and / or methyl acetate. As well as
(C) During the oxidation, the following operating ratios in the following specific ranges:
(I) maintaining the ratio of the number of moles of carbon oxide produced to the number of moles of said aromatic compound supplied in the range of about 0.02: 1 to about 0.24: 1;
(Ii) maintaining the ratio of the number of moles of carbon dioxide produced to the number of moles of aromatic compound supplied in the range of about 0.01: 1 to about 0.21: 1;
(Iii) maintaining a ratio of moles of the carbon monoxide produced to moles of the aromatic compound fed in the range of about 0.005: 1 to about 0.09: 1;
(Iv) maintaining the ratio of the number of moles of the methyl acetate produced to the number of moles of the aromatic compound fed in the range of about 0.005: 1 to about 0.09: 1;
Maintaining one or more of the methods.
[2] maintaining the ratio of the number of moles of carbon oxide produced to the number of moles of the aromatic compound fed in the range of about 0.02: 1 to about 0.24: 1 1].
[3] maintaining the ratio of the number of moles of carbon dioxide produced to the number of moles of aromatic compound supplied in the range of about 0.01: 1 to about 0.21: 1. 1].
[4] maintaining the ratio of moles of the carbon monoxide produced to moles of the aromatic compound supplied in the range of about 0.005: 1 to about 0.09: 1. The method according to [1].
[5] maintaining the ratio of the number of moles of the methyl acetate produced to the number of moles of the aromatic compound fed in the range of about 0.005: 1 to about 0.09: 1. 1].
[6] Maintaining the ratio of the number of moles of carbon oxide produced to the number of moles of the aromatic compound supplied in the range of about 0.02: 1 to about 0.24: 1 Maintaining the ratio of moles of carbon dioxide to moles of the aromatic compound supplied in the range of about 0.01: 1 to about 0.21: 1 and the number of moles of carbon monoxide produced. Maintaining the ratio to moles of the aromatics fed in the range of about 0.005: 1 to about 0.09: 1, and feeding the aromatics of moles of methyl acetate produced The method of [1] above, wherein the ratio to the number of moles is maintained in the range of about 0.005: 1 to about 0.09: 1.
[7] The method according to [1] above, wherein at least one of the operation ratios is maintained for at least 12 hours.
[8] The method according to [1] above, wherein at least two of the operation ratios are maintained for at least 12 hours.
[9] The method according to [1] above, wherein at least three of the operation ratios are maintained for at least 12 hours.
[10] The method according to [1] above, wherein all the operation ratios are maintained for at least 12 hours.
[11] Maintaining the ratio of the number of moles of carbon oxide produced to the number of moles of the aromatic compound supplied in the range of about 0.05: 1 to about 0.19: 1 Maintaining the ratio of moles of carbon dioxide to moles of the aromatic compound supplied in the range of about 0.04: 1 to about 0.16: 1; Maintaining said ratio to moles of said aromatics fed in a range of about 0.015: 1 to about 0.05: 1, and feeding said aromatics of moles of said methyl acetate produced The method of [1] above, wherein the ratio to the number of moles is maintained in the range of about 0.01: 1 to about 0.07: 1.
[12] The method according to [1] above, wherein all the operation ratios are maintained for at least 36 hours.
[13] Said [1 ] Method.
[14] The method according to [1] above, wherein the aromatic compound is para-xylene.
[15] The method according to [1], wherein the oxidation converts at least about 50 mole percent of the aromatic compound to terephthalic acid.
[16] The method of [1] above, wherein the oxidation causes at least about 10 weight percent of the aromatic compound to form a solid in the reaction medium.
[17] The method of [1] above, wherein the oxidation generates heat and less than about 50 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface.
[18] The method of [1] above, comprising supplying an oxidant stream to the oxidation reactor, wherein the oxidant stream comprises less than about 50 mole percent molecular oxygen.
[19] The method according to [1] above, wherein the oxidation reactor is a bubble column reactor.
[20] The method according to [1] above, wherein the reaction medium includes a solid phase, a liquid phase, and a gas phase.
[21] The aromatic compound is para-xylene, the oxidation converts at least about 90 mole percent of the para-xylene to terephthalic acid, and the oxidation results in at least about 50 weight percent of the para-xylene being in the reaction medium. Forming solid terephthalic acid, heat is generated by the oxidation, and less than about 30 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface, and the method includes transferring an oxidant stream to the reactor. The method of [1] above, wherein the oxidant stream comprises about 15 to about 30 mole percent molecular oxygen.
[22] The method according to [1] above, wherein the concentration of p-toluic acid in the liquid phase of the reaction medium is less than about 8,000 ppmw.
[23] further comprising removing slurry from the oxidation reactor, wherein the slurry comprises a liquid mother liquor and solid particles of the crude terephthalic acid, and the representative sample of the slurry is based on a combined solid and liquid slurry component The following features:
(V) containing less than about 1,500 ppmw isophthalic acid (IPA);
(Vi) containing less than about 500 ppmw phthalic acid (PA),
(Vii) containing less than about 500 ppmw trimellitic acid (TMA),
(Viii) comprises less than about 2,000 ppmw benzoic acid (BA),
The method according to [1] above, comprising one or more of the following.
[24] The amount of carbon dioxide in the dry offgas from the oxidation reactor ranges from about 0.1 to about 1.5 mole percent, and the amount of carbon monoxide in the dry offgas from the oxidation reactor. The amount ranges from about 0.05 to about 0.6 mole percent and the amount of molecular oxygen in the dry offgas from the oxidation reactor ranges from about 0.1 to about 6 mole percent. 1].
[25] The method according to [1] above, wherein the molar residual ratio of the aromatic compound via the reaction medium is in the range of about 98 to about 99.9 percent.
[26] The method according to [1] above, wherein the oxidation is performed in the presence of a catalyst system containing cobalt.
[27] The method according to [17] above, wherein the catalyst system further comprises bromine and manganese.
[28] A substantial portion of the crude terephthalic acid is present as solid particles, and a representative sample of the crude terephthalic acid particles has the following characteristics:
(Ix) comprising less than about 12 ppmw of 4,4-dicarboxystilbene (4,4-DCS);
(X) containing less than about 800 ppmw isophthalic acid (IPA);
(Xi) less than about 100 ppmw 2,6-dicarboxyfluorenone (2,6-DCF),
(Xii) the percent transmission at 340 nanometers (% T ₃₄₀ ) is greater than about 25;
The method according to [1] above, comprising one or more of the following.
[29] A substantial portion of the crude terephthalic acid is present as solid particles and a representative sample of the crude terephthalic acid particles is at least in THF for 1 minute when subjected to a timed dissolution test as defined herein. The method according to [1] above, wherein the method is dissolved at a concentration of about 500 ppm.
[30] A substantial portion of the crude terephthalic acid is present as solid particles and a representative sample of the crude terephthalic acid has a time constant “C” determined by a timed dissolution model as defined herein of about 0.5. The method according to [1] above, which exceeds the reciprocal minutes.
[31] The method according to [1], further comprising oxidizing at least a part of the crude terephthalic acid in a secondary oxidation reactor.
[32] (a) supplying an aromatic compound to the oxidation reactor;
(B) generating crude terephthalic acid by oxidizing at least a portion of the aromatic compound in the liquid phase of the multiphase reaction medium contained in the oxidation reactor; and
(C) maintaining a molar residual ratio of the aromatic compound greater than about 98 percent during the oxidation;
Including methods.
[33] The method of [32] above, wherein the molar residual ratio is maintained in the range of about 98.5 to about 99.8 percent.
[34] The method of [32] above, wherein the molar residual ratio is maintained in the range of about 99 to about 99.7 percent.
[35] Said [32 ] Method.
[36] The method of [32] above, wherein the oxidation converts at least about 50 mole percent of the aromatic compound to terephthalic acid.
[37] The method of [32] above, wherein the oxidation causes at least about 10 weight percent of the aromatic compound to form a solid in the reaction medium.
[38] The method of [32] above, wherein the oxidation generates heat and less than about 50 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface.
[39] The method of [32] above, comprising feeding an oxidant stream to the oxidation reactor, wherein the oxidant stream comprises less than about 50 mole percent molecular oxygen.
[40] The method according to [32], wherein the molar residual ratio is maintained for at least 12 hours.
[41] The method according to [32] above, wherein the oxidation reactor is a bubble column reactor.
[42] The method according to [32] above, wherein the reaction medium comprises a solid phase, a liquid phase, and a gas phase.
[43] The aromatic compound is para-xylene, the oxidation converts at least about 90 mole percent of the para-xylene to terephthalic acid, and the oxidation results in at least about 50 weight percent of the para-xylene being in the reaction medium. Forming solid terephthalic acid, heat is generated by the oxidation, and less than about 30 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface, and the method includes transferring an oxidant stream to the reactor. The method of [32] above, wherein the oxidant stream comprises about 15 to about 30 mole percent molecular oxygen and the molar residual ratio is maintained for at least 36 hours.
[44] The method according to [32] above, wherein the concentration of p-toluic acid in the liquid phase of the reaction medium is less than about 8,000 ppmw.
[45] The method according to [32] above, wherein the oxidation is carried out in the presence of a catalyst system containing cobalt, bromine and manganese.
[46] The method according to [32], further comprising oxidizing at least a part of the crude terephthalic acid in a secondary oxidation reactor.

Claims

(A) supplying an aromatic compound to the oxidation reactor;
(B) Producing crude terephthalic acid by oxidation of producing at least part of the aromatic compound in the liquid phase of the multiphase reaction medium contained in the oxidation reactor to produce carbon dioxide, carbon monoxide, and / or methyl acetate. And (c) during the oxidation, the following operating ratios of the following specific ranges:
(I) The ratio of the number of moles of carbon oxide produced to the number of moles of the aromatic compound supplied is set to 0 . 02: 1 or, et al. 0. Maintaining in the 24: 1 range,
(Ii) the number of moles of the carbon dioxide produced, the ratio moles of said aromatic compound fed, 0. 01: 1 or, et al. 0. Maintaining in the 21: 1 range,
(Iii) The ratio of the number of moles of the carbon monoxide produced to the number of moles of the aromatic compound supplied is 0 . 005: 1 or et al. 0. Maintaining a range of 09: 1,
(Iv) The ratio of the number of moles of the methyl acetate produced to the number of moles of the aromatic compound supplied is 0 . 005: 1 or et al. 0. Maintaining a range of 09: 1,
Maintaining one or more of the methods.

The ratio of the number of moles of carbon oxide produced to the number of moles of the aromatic compound supplied is 0 . 02: 1 or, et al. 0. 24: maintained at 1, and the ratio to the number of moles of said aromatic compound fed in the number of moles of the carbon dioxide produced 0. 01: 1 or, et al. 0. 21: maintained at 1, and the ratio number of moles the supplied the aromatic compounds of the carbon monoxide generated 0. 005: 1 or et al. 0. 09: maintained at 1, and the ratio to the number of moles of supplied of the number of moles of the methyl acetate produced the aromatic compound 0. 005: 1 or et al. 0. The method of claim 1, wherein the method is maintained in the range of 09: 1.

The method of claim 1, wherein at least three of the operating ratios are maintained for at least 12 hours.

The method of claim 1, wherein the aromatic compound is para-xylene.

The method of claim 1, wherein the oxidation generates heat and less than 50 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface.

The method of claim 1, wherein the oxidation reactor is a bubble column reactor.

The aromatic compound is para-xylene, said 9 0 mole percent and less of the para-xylene by oxidation into a terephthalic acid, wherein the paraxylene least five 0 weight percent in the reaction medium by oxidation Solid terephthalic acid is formed on the substrate, heat is generated by the oxidation, and less than 30 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface, the method comprising: comprising supplying to said oxidant stream comprises one five et 3 0 mole percent molecular oxygen, the method according to claim 1.

Removing a slurry from the oxidation reactor, the slurry comprising a liquid mother liquor and solid particles of the crude terephthalic acid, a representative sample of the slurry based on the combined solid and liquid slurry components: Features:
(V ) comprises less than 1,500 ppmw isophthalic acid (IPA),
(Vi ) containing less than 500 ppmw phthalic acid (PA),
(Vii ) containing less than 500 ppmw trimellitic acid (TMA),
(Viii ) containing less than 2,000 ppmw benzoic acid (BA),
The method of claim 1, comprising one or more of:

The amount of carbon dioxide in the dry offgas from the oxidation reactor is 0 . 1 or et al. 1. In the range of 5 mole percent, and the amount of carbon monoxide in the dry offgas from the oxidation reactor is 0 . 05 et al. 0. In the range of 6 mole percent and the amount of molecular oxygen in the dry off-gas from the oxidation reactor is 0 . In the range of 1 or et 6 mole percent, The method of claim 1.

The molar survival ratio of the aromatic compound via the reaction medium is in the range of 9 8 through 9 9.9 percent, The method of claim 1.

A substantial portion of the crude terephthalic acid is present as solid particles, and a representative sample of the crude terephthalic acid particles has the following characteristics:
(Ix ) comprising less than 12 ppmw of 4,4-dicarboxystilbene (4,4-DCS),
(X ) containing less than 800 ppmw of isophthalic acid (IPA),
(Xi ) comprises less than 100 ppmw of 2,6-dicarboxyfluorenone (2,6-DCF),
(Xii) 340 percent transmission at the nanometer (% T ₃₄₀₎ is more than 2 5,
The method of claim 1, comprising one or more of:

Wherein a substantial portion of the crude terephthalic acid is present as solid particles, a representative sample of the crude terephthalic acid particles, when subjected to the timed dissolution test defined herein, 5 also less in THF at 1 minute The method of claim 1, wherein the method is dissolved at a concentration of 00 ppm.

A substantial portion of the crude terephthalic acid is present as solid particles, and a time constant “C” of a representative sample of the crude terephthalic acid determined by a timed dissolution model as defined herein is 0 . The method of claim 1, wherein the method exceeds 5 reciprocals.

(A) supplying an aromatic compound to the oxidation reactor;
(B) generating crude terephthalic acid by oxidizing at least a portion of the aromatic compound in the liquid phase of the multiphase reaction medium contained in the oxidation reactor; and (c) during the oxidation, Maintaining the molar residual ratio of aromatics above 98 percent;
Including methods.

Maintaining the molar survival ratio in the range of 9 9 through 9 9.7% The method of claim 14.

15. The method of claim 14 , wherein the molar residual ratio is maintained for at least 12 hours.

The method of claim 14 , wherein the oxidation reactor is a bubble column reactor.

The aromatic compound is para-xylene, the is converted to terephthalic acid 90 mole percent and less of the paraxylene by oxidation, the least of five 0 weight percent said reaction medium of the para-xylene by the oxidation Forming solid terephthalic acid, heat is generated by the oxidation, and less than 30 percent of the heat generated by the oxidation is removed from the reaction medium by a heat exchange surface, and the method includes transferring an oxidant stream to the reactor. comprising supplying said oxidant stream comprises molecular oxygen 1 5 or et 3 0 mole percent, maintaining the molar survival ratio of at least 36 hours a method according to claim 14.

The method of claim 14 , further comprising oxidizing at least a portion of the crude terephthalic acid in a secondary oxidation reactor.